CN103638942B - SCR (selective catalytic reduction) catalyst for denitrating low-temperature smoke of cement kiln and preparation method thereof - Google Patents
SCR (selective catalytic reduction) catalyst for denitrating low-temperature smoke of cement kiln and preparation method thereof Download PDFInfo
- Publication number
- CN103638942B CN103638942B CN201310693174.6A CN201310693174A CN103638942B CN 103638942 B CN103638942 B CN 103638942B CN 201310693174 A CN201310693174 A CN 201310693174A CN 103638942 B CN103638942 B CN 103638942B
- Authority
- CN
- China
- Prior art keywords
- scr catalyst
- active component
- carrier
- catalyst
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention provides an SCR (selective catalytic reduction) catalyst for denitrating low-temperature smoke of a cement kiln and a preparation method thereof. The SCR catalyst is characterized in that by adjusting the technological conditions such as proportions of active components, mass ratio of carriers and active components, calcining temperature and the like, a composite metal oxide which is formed by one or more metal elements out of manganese (Mn), ferrum (Fe), copper (Cu), cerium (Ce), lanthanum (La), bismuth (Bi), niobium (Nb), tantalum (Ta) and the like is loaded on a carrier by adopting an impregnation method, and tungsten and molybdate are used as active assistants. The active components in the SCR catalyst are uniformly distributed on the surface of the carrier in an unformed shape, the low-temperature activity of the catalyst is improved by utilizing the synergistic effect of multiple metals, the SCR catalyst is particularly suitable for the denitration of the smoke which is discharged from a dust collector on the tail of the cement kiln, the denitration rate can reach higher than 70 percent at the temperature of 80 DEG C, the denitration rate is higher than 90 percent in the temperature range of 125 DEG C to 200 DEG C, and the toxicity resistance is strong.
Description
Technical field
The invention belongs to the catalyst in nitrogen oxides technical field of emission reduction in cement industry, more particularly to one kind are used for
The catalyst based on SCR (scr) technology of the low-temperature denitration of flue gas after cement kiln tail deduster and
Its preparation method.
Background technology
The reinforcement to cement industry discharged nitrous oxides control dynamics for the country during with " 12 ", simple low nitrogen
Combustion technology is difficult to meet the requirement of the discharge standard of increasingly stringent.SCR (scr) technology refers to
In the presence of catalyst, using reducing agent (as nh3, liquefied ammonia, urea) " selective " with flue gas in nox
React and generate the n of nontoxic pollution-free2And h2o.The core of this technology is scr catalyst, and its performance directly determines
Denitration effect and the application of technology.Scr technology because having the advantages that high denitration rate, high selectivity, safe and reliable,
It is used widely in coal-fired power station boiler.However, due to lacking applicable catalysis material, scr technology is at home and abroad
Application case in cement kiln is little.
At present, the active temperature of commercial vanadium Titanium series catalyst is 300-450 DEG C, only has suspended preheater in cement kiln
The flue-gas temperature in one-level (c1) exit can meet this requirement, but the dust in flue gas, alkaline earth/alkali metal, so2
Content is all higher, easily causes blocking, the poisoning of catalyst, or even loses efficacy.It is additionally, since China's major part cement life
Producing line is all mounted with boiler of power generation by waste heat in cl outlet, and the installation of scr can substantially reduce residual heat generating efficiency, be unfavorable for
The energy-saving and emission-reduction of enterprise.
After the ideal position of installation scr catalyst is in kiln tail deduster in cement kiln, make exhaust gas dust content
It is reduced to 50mg/m3Hereinafter, be conducive to extending the service life of catalyst, save and reduce discharging cost.But, this cloth
The mode of putting cannot avoid the too low problem of flue-gas temperature, and temperature after deduster for the usual cement kiln exit gas exists
120 DEG C about.The use condition reaching commercial catalyst by the way of heating again can increase reduction of discharging cost, system energy
Consumption and operating cost.On the other hand, in view of the feature of cement clinker production technology, kiln exit gas after deduster still
Containing higher so2, alkali/alkaline earth metal, h2O etc..Therefore, for cement kiln exit gas working condition, research
There is greater activity, high resist toxic scr catalyst to have important economy and practical significance with exploitation.Existing special
In sharp document, the Chinese invention patent application of only Application No. 201110402436.x provides one kind and is used for cement
The technique of kiln gas denitration, is directed to the low temperature scr catalyst after cement kiln tail deduster.This invention is
First reducing agent (ammoniacal liquor, urea etc.) is sprayed in the cement kiln flue gas that temperature is 750-1100 DEG C and mix, make flue gas
In nitrogen oxides major part be reduced to n2, then reducing agent and the nitrogen oxides that is not reduced through cooling, humidification,
Enter scr reactor after dedusting, on the surface of scr catalyst, selective catalytic reduction reaction occurs, nitrogen oxides
Removal efficiency reaches more than 90%.Used in this invention, cellular scr catalyst is still belonging to traditional vanadium titanium system,
Raw material vanadic anhydride has toxicity, easily produces harm to human body, does not meet the former of the green production that today's society is advocated
Then, the content and passing through nitrogen oxides in the kiln gas in scr reactor in this invention is few, and catalyst is in high concentration
Nitrogen oxides atmosphere under low-temperature catalytic activity and anti-Poisoning tested.
Mn series catalysts are low-temperature catalytic activity preferable scr catalyst, such as mnox-ceo2、mnox/tio2、mnox/
Activated carbon etc., shows excellent catalysis activity below 200 DEG C.The relevant mn series catalysts reported in document at present
Research in mostly be powder catalyst, because this kind of catalyst does not possess certain shape and mechanical strength, away from actual should
With ([1] qi g, yang r t, chang r.mno farther outx-ceo2mixed oxides prepared by
coprecipitation for selective catalytic reduction of no with nh3at low
temperatures.applied catalysis b:environmental,2004,51:93-106.[2]wang
yanli,gechuanzhang,zhan liang,et al,mnox-ceo2/activated carbon honeycomb
catalyst for selective catalytic reduction of no with nh3at low temperature,
Industrial and engineering chemistry research, 2012,51 (36): 11,667 11673
[3]li j,chang h,ma l.low temperature selective catalytic reduction of no
with nh3over metal oxide and zeolite catalysts-a review.catalyss today,2011,
175 (1): 147-156.).Patent document about low temperature scr catalyst (cn102489294a, cn101011659,
Cn103127951a etc.) it is all that flue gas condition for coal-burning power plant or Diesel engine is designed and developed.However, water
Mud clinker burning technique determines miscellaneous containing a large amount of alkali metal, alkaline-earth metal, hydroxide ion etc. in cement kiln end flue gas
Matter, therefore, proposes brand-new and higher requirement to the anti-Poisoning of catalyst.
Content of the invention
It is an object of the invention to provide a kind of low-temperature denitration of flue gas after deduster for cement kiln tail based on selection
Property catalysis reduction (scr) technology catalyst.
Scr catalyst for cement kiln tail low-temperature denitration of flue gas provided by the present invention, is to load active component
Carrier prepares, described active component be manganese (mn) and manganese with selected from tungsten (w), molybdenum (mo), iron
(fe), in copper (cu), cerium (ce), lanthanum (la), bismuth (bi), niobium (nb) and tantalum (ta) etc.
Kind or the combination of multiple element.
The percentage that active component accounts for the catalyst total quality including carrier is 5wt%-25wt%, optional 5wt
The combination of any number between %-15wt% or 15wt%-25wt%.
The mol ratio that manganese (mn) element accounts for the total element of active component is 60%-95 for 0.6-0.95(molar percentage
%), preferably 0.7-0.9(molar percentage is 70%-90%).
Manganese (mn), iron (fe), copper (cu), cerium (ce), lanthanum (la), the presoma of bismuth (bi) can be
Chlorate, nitrate or acetate, the presoma of niobium (nb) and tantalum (ta) is oxide niobium pentaoxide (nb2o5)
Or tantalum pentoxide (ta2o5), the presoma of tungsten (w) and molybdenum (mo) is polyacid ammonia salt, concretely ammonium molybdate,
Ammonium paramolybdate, ammonium tetramolybdate, ammonium tungstate, ammonium metatungstate etc..
In active component, each element molar percentage can be respectively: tungsten (w) 2%-30%, molybdenum (mo) 2%-30%,
Iron (fe) 5%-40%, copper (cu) 5%-40%, cerium (ce) 5%-40%, lanthanum (la) 5%-40%, bismuth
(bi) 5%-40%, niobium (nb) 5%-40%, tantalum (ta) 5%-40%；Above each element is in the range of being limited
Single use or in combination of two or more use, and the consumption of total amount and manganese (mn) 60%-95% adds and is active component
Total mole number 100%.
Described carrier can be: by titanium dioxide (tio2), alchlor (al2o3), zirconium dioxide (zro2),
Silica (sio2) etc. the powder that assembles of one or more of oxide and h2O, cmc(hydroxymethyl cellulose),
Mea(monoethanolamine) mixed according to the mass ratio of 100:10:1:1, agglomerating, after extrusion molding, dry, then
Obtain after calcining 2-10h at 500-1200 DEG C.
Described scr catalyst has anti-so2Poisoning and steam-resistant poisoning performance.
Another object of the present invention be provide one kind prepare claim 1-7 arbitrary described for cement kiln tail low temperature cigarette
The method of the scr catalyst of qi exhaustion nitre.
The method is to load to active component by infusion process to be obtained on carrier, specifically can comprise the following steps that
1) prepare carrier
By titanium dioxide (tio2), alchlor (al2o3), zirconium dioxide (zro2), silica (sio2)
The powder assembling Deng one or more of oxide and h2O, cmc(hydroxymethyl cellulose), mea(monoethanolamine)
Mass ratio according to 100:10:1:1 is mixed, agglomerating, after extrusion molding, dries, then at 500-1200 DEG C
Obtain after calcining 2-10h；
2) preparation of active component mixed aqueous solution
Design loading by carrier and calculate each element forerunner's weight in required active component, prepare and contain active component
Mixed aqueous solution, make active component in mixed aqueous solution (presoma) mass percentage concentration be 5wt%-50wt
%；
3) load of active component
Carrier is put in active component mixed aqueous solution immersion 1-6h, after the complete loaded body absorption of solution to be impregnated,
Dry at 50-120 DEG C, then calcine 2-10h at 200-800 DEG C, obtain scr catalyst.
Aforementioned scr catalyst carries out the application in denitration in the low-temperature flue gas after deduster to cement kiln exit gas
Fall within the present invention.Described application, installs catalytic reduction reaction device additional, in device after the deduster of cement kiln tail
It is mounted with described scr catalyst, with scr catalyst, denitration is carried out to low-temperature flue gas.
The present invention is obtained by the manganese systems metal composite oxide that infusion process loads as active component on shaping carrier
Scr catalyst be applied to low-temperature denitration of flue gas after deduster for the cement kiln exit gas, described low-temperature flue gas
Main component includes o2、co2, nox, a small amount of so2And vapor, and containing a small amount of dust granules and alkali gold
Belong to impurity, now generally below 120 DEG C of flue-gas temperature；By scr catalyst in the experiment test present invention to low temperature cigarette
The denitration effect of gas.
After testing, the scr catalyst of the present invention can reach more than 70%, 125-200 DEG C of temperature in 80 DEG C of denitration rate
In the range of degree, denitration rate is more than 90%, and has stronger anti-Poisoning.
The invention provides a kind of scr catalyst for cement kiln low-temperature denitration of flue gas, and by adjusting activearm
/ the mass ratio of proportioning, carrier and active component, the process conditions such as calcining heat, it is further provided a kind of
The method preparing this scr catalyst, using infusion process supported on carriers manganese (mn) and iron (fe), cerium (ce),
The metal composite oxide that one or more of metallic elements such as bismuth (bi), niobium (nb) are formed.The scr of the present invention
In catalyst, active component is uniformly distributed in carrier surface with unformed shape, using many metals synergy, improves and urges
The low temperature active of agent, is particularly well-suited to the denitrating flue gas after cement kiln tail deduster, can reach in 80 DEG C of denitration rates
Denitration rate in more than 70%, 125-200 DEG C of temperature range is more than 90%, and has stronger anti-Poisoning.
Brief description
Fig. 1 is the xrd collection of illustrative plates of the scr catalyst sample of embodiment 1,5,9 preparation
Fig. 2 is scr catalyst to the denitration effect experiment test device of low-temperature flue gas and workflow
Fig. 3 is the denitration curve of the scr catalyst sample of embodiment 1,5,9 preparation
Fig. 4 is anti-poisoning (so to cement kiln low-temperature flue gas for the scr catalyst2Poisoning and water vapour poisoning) performance test
Test device and workflow
Fig. 5 is so2With the impact to scr catalyst denitration performance prepared by embodiment 1,5,9 for the water vapour
Specific embodiment
It is contemplated that for the low-temperature denitration of flue gas after cement kiln tail deduster, providing a kind of scr catalyst.
Anti- Poisoning is the key factor of catalyst performance.The present invention is directed to cement kiln end flue gas, it is usually required mainly for consider anti-
so2Poisoning and steam-resistant poisoning performance.So under low temperature2The poisoning effect of catalyst can be significantly increased, special flue gas
In contain h2During o.Clinker burning and sack cleaner are respectively provided with certain sulfur fixation and desulfidation, therefore water
The generally uneasy dress desulphurization system of stall, still also contains a certain amount of so after kiln exit gas removing dust2.
Research finds, in commercial Application based on integer catalyzer, integer catalyzer typically refer to those have many narrow
Narrow, the straight or overall structure catalyst of the parallel channels of bending, adopts honeycomb fashion or plank frame more.Compare biography
System pellet type catalyst, integer catalyzer has the remarkable advantage of three aspects, and first, it has relatively low pressure drop, energy
Reduce the generation of bed heat spot；Secondly, it has good mechanical performance；Again, it has big geometrical surface,
Diffusion length is short etc., it has also become one of the most potential research direction in current heterogeneous catalysis field.Overall catalysis
Agent is mainly made up of active component, co-catalyst, dispersion carrier and skeleton matrix etc..Active component be loaded with impregnate
The methods such as method, ion-exchange, deposition-precipitation, sol-gel process.It is most commonly that and use active component presoma
Solution impregnation Second support coating, then dry, roasting be transformed into active specy.
Infusion process is to prepare a kind of common method of multicomponent catalyst, and the method is to have certain profile and size
Strip, board-like and cellular etc. as carrier material, the solubility salt being impregnated in active component is made into the aqueous solution
(as mn (no3)2, ce(no3), if load one layer or dried layer active component coating, it is commonly used for preparing vehicle exhaust
Disposal three-way catalyst.Because active component is all distributed in carrier surface, can increase operation rate and be easy to inactivate
Regeneration.On the other hand, adsorption process is the committed step of heterogeneous catalytic reaction, to the reactivity of catalyst and anti-in
Toxicity all has important effect.Tungsten polyacid generally has special structure, excellent absorption property and redox
Ability, is the important new catalytic material of a class.
Studied based on above, the present invention finally determines scr catalyst and its system for cement kiln low-temperature denitration of flue gas
Preparation Method.
The present invention is used for the scr catalyst of cement kiln tail low-temperature denitration of flue gas, is that active component is supported on carrier
Prepare, described active component be manganese (mn) and manganese with selected from tungsten (w), molybdenum (mo), iron (fe),
One or more of copper (cu), cerium (ce), lanthanum (la), bismuth (bi), niobium (nb) and tantalum (ta) etc.
The combination of element.
The percentage that described active component accounts for the catalyst total quality including carrier is 1wt%-30wt%, excellent
Select 5%-25%.
The mol ratio that manganese (mn) element accounts for the total element of active component is 60%-95% for 0.6-0.95(molar percentage),
Preferably 0.7-0.9(molar percentage is 70%-90%).
Manganese (mn), iron (fe), copper (cu), cerium (ce), lanthanum (la), the presoma of bismuth (bi) can be
Chlorate, nitrate or acetate, the presoma of niobium (nb) and tantalum (ta) is oxide niobium pentaoxide (nb2o5)
Or tantalum pentoxide (ta2o5), the presoma of tungsten (w) and molybdenum (mo) is polyacid ammonia salt, concretely ammonium molybdate,
Ammonium paramolybdate, ammonium tetramolybdate, ammonium tungstate, ammonium metatungstate etc..
In described active component, each element molar percentage can be respectively:
Above each element is single in the range of being limited to be used or in combination of two or more use, total amount and manganese (mn) 60
The consumption of %-95% adds and is active component total mole number 100%.
Described carrier can be: by titanium dioxide (tio2), alchlor (al2o3), zirconium dioxide (zro2),
Silica (sio2) etc. the powder that assembles of one or more of oxide and h2O, cmc(hydroxymethyl cellulose),
Mea(monoethanolamine) mixed according to the mass ratio of 100:10:1:1, agglomerating, after extrusion molding, dry, then
Obtain after calcining 2-10h at 500-1200 DEG C.
The scr catalyst of the present invention has anti-so2Poisoning and steam-resistant poisoning performance.
The above-mentioned scr catalyst for cement kiln tail low-temperature denitration of flue gas of the present invention, is by activearm by infusion process
Divide to load to and be obtained on carrier, specifically can comprise the following steps that
1) prepare carrier
By titanium dioxide (tio2), alchlor (al2o3), zirconium dioxide (zro2), silica (sio2)
The powder assembling Deng one or more of oxide and h2O, cmc(hydroxymethyl cellulose), mea(monoethanolamine)
Mass ratio according to 100:10:1:1 is mixed, agglomerating, after extrusion molding, dries, then at 500-1200 DEG C
Obtain after calcining 2-10h；
2) preparation of active component mixed aqueous solution
Design loading by carrier and calculate each element forerunner's weight in required active component, prepare and contain active component
Mixed aqueous solution, make active component in mixed aqueous solution (presoma) mass percentage concentration be 5wt%-50wt
%；
3) load of active component
Carrier is put in active component mixed aqueous solution immersion 1-6h, after the complete loaded body absorption of solution to be impregnated,
Dry at 50-120 DEG C, then calcine 2-10h at 200-800 DEG C, obtain scr catalyst.
Scr catalyst carries out the application in denitration in the low-temperature flue gas after deduster to cement kiln exit gas and also belongs to
In protection scope of the present invention.
The method carrying out denitration to low-temperature flue gas after deduster for the cement kiln exit gas is: in cement kiln tail
Install catalytic reduction reaction device after deduster additional, in device, be mounted with described scr catalyst, with scr catalyst to low
Warm flue gas carries out denitration.
Describe in detail with reference to embodiments.
Embodiment is implemented under premised on technical solution of the present invention, gives detailed embodiment and specific
Operating process, embodiment will be helpful to understand the present invention, but protection scope of the present invention is not limited to following embodiments.
Percent concentration described in embodiment be if no special instructions mass/mass (w/w, unit g) percent concentration,
Mass/volume (w/v, unit g/100ml) percent concentration or volume/volume (v/v, units/ml) percent concentration.
Embodiment 1, preparation scr catalyst
The preparation of scr catalyst comprises the following steps:
1st, prepare carrier
Pure titinium dioxide (tio will be analyzed2) powder and h2O, cmc(hydroxymethyl cellulose), mea(monoethanolamine)
Mixed Deng the mass ratio according to 100:10:1:1, agglomerating, extrusion molding, obtained strip carrier, dry at 60 DEG C
Dry in dry case, be subsequently placed in Muffle furnace and calcine 6h(2-10h in 1000 DEG C (500-1200 DEG C)),
Obtain carrier.
2nd, the load of active component
1) according to step 1, choose the strip carrier of uniform size of its certain mass, account for including carrier by active component
It is 15wt% in the percentage of interior catalyst total quality, manganese (mn) element accounts for the mol ratio of the total element of active component
For 0.75(molar percentage be 75%) requirement, calculate required for the manganese (mn) as active component, cerium
(ce), the quality of the nitrate of bismuth (bi), by manganese nitrate, cerous nitrate, bismuth nitrate according to mol ratio 15:4:1
Proportions mixed aqueous solution, add oxalic acid or citric acid as complexing agent, react with active ingredients substances,
Form complex solution, the mass percentage concentration of complex solution mesoxalic acid or citric acid is 1wt%, activearm
The mass percentage concentration dividing (manganese nitrate, cerous nitrate, bismuth nitrate) is 10wt%；
2) carrier is put into and in complex solution (dipping solution), soaks 6h(1-6h), solution to be impregnated
Completely after loaded body absorption, in 80 DEG C of (50-120 DEG C) drying boxes, 4h is dried, then at 500 DEG C (200-800 DEG C
) under calcine 6h(2-10h), obtain scr catalyst.
Embodiment 2, preparation scr catalyst
Comprise the following steps:
1st, prepare carrier
Pure titinium dioxide (tio will be analyzed2) powder and silica (sio2) powder and h2O, cmc(methylol is fine
Dimension element), mea(monoethanolamine) etc. mixed according to the mass ratio of 50:50:10:1:1, agglomerating, extrusion molding,
Obtain strip carrier, dry in 60 DEG C of drying boxes, be subsequently placed in that in Muffle furnace, (500-1200 DEG C all in 1000 DEG C
Can) calcining 4h(2-10h), obtain carrier.
2nd, the load of active component
Same as Example 1.
Embodiment 3, preparation scr catalyst
Comprise the following steps:
1st, prepare carrier
Pure titinium dioxide (tio will be analyzed2) powder and alchlor (al2o3) powder and h2O, cmc(methylol is fine
Dimension element), mea(monoethanolamine) etc. mixed according to the mass ratio of 50:50:10:1:1, agglomerating, extrusion molding,
Obtain honeycomb support, dry in 60 DEG C of drying boxes, be subsequently placed in Muffle furnace and calcine 6h in 1000 DEG C, obtain
Carrier.
2nd, the load of active component
Same as Example 1.
Embodiment 4, preparation scr catalyst
Comprise the following steps:
1st, prepare carrier
Pure titinium dioxide (tio will be analyzed2) powder and zirconium dioxide (zro2) powder and h2O, cmc(methylol is fine
Dimension element), mea(monoethanolamine) etc. mixed according to the mass ratio of 50:50:10:1:1, agglomerating, extrusion molding,
Obtain honeycomb support, dry in 60 DEG C of drying boxes, be subsequently placed in Muffle furnace in 1000 DEG C (500-1200 DEG C
) calcining 6h(2-10h), obtain carrier.
2nd, the load of active component
Same as Example 1.
Embodiment 5, preparation scr catalyst
Comprise the following steps:
1st, prepare carrier
Same as Example 1.
2nd, the load of active component
1) according to step 1, choose the strip carrier of uniform size of its certain mass, account for including carrier by active component
It is 25wt% in the percentage of interior catalyst total quality, manganese (mn) element accounts for the mol ratio of the total element of active component
For 0.9(molar percentage be 90%) requirement, calculate required for the manganese acetate as active component, cerous nitrate,
Niobium pentaoxide (nb2o5) quality, by nb2o5Mix with a small amount of hydrofluoric acid, under the conditions of 60-120 DEG C, promote it
It is completely dissolved, then by nb2o5, manganese acetate, cerous nitrate according to mol ratio 1:18:1 proportions mix water-soluble
Liquid, adds oxalic acid or citric acid to form complex solution, wherein, the quality hundred of oxalic acid or citric acid as complexing agent
Point concentration is 20wt%(10wt%-40wt%), active component (manganese acetate, cerous nitrate, niobium pentaoxide)
Mass percentage concentration be 40wt%；
2) carrier is put in complex solution immersion 5h(1-6h), the complete loaded body of solution to be impregnated is inhaled
Attached, 4h is dried in 80 DEG C of (50-120 DEG C) drying boxes, then under 500 DEG C (200-800 DEG C)
Calcining 6h(2-10h), obtain scr catalyst.
Embodiment 6, preparation scr catalyst
Comprise the following steps:
1st, prepare carrier
Same as Example 2.
2nd, the load of active component
Same as Example 5, only by niobium pentaoxide (nb2o5) replace with tantalum pentoxide (ta2o5).
Embodiment 7, preparation scr catalyst
Comprise the following steps:
1st, prepare carrier
Same as Example 3.
2nd, the load of active component
Same as Example 5.
Embodiment 8, preparation scr catalyst
Comprise the following steps:
1st, prepare carrier
Same as Example 4.
2nd, the load of active component
Same as Example 5.
Embodiment 9, preparation scr catalyst
Comprise the following steps:
1st, prepare carrier
Same as Example 1.
2nd, the load of active component
1) carrier being obtained according to step 1, is accounted for hundred of the catalyst total quality including carrier by active component
Divide than being 5wt%, the mol ratio that manganese (mn) element accounts for the total element of active component is 70% for 0.7(molar percentage)
Requirement, calculate required for the manganese nitrate as active component, ferric nitrate, ammonium paramolybdate ((nh4)6mo7o24) with
And the quality of niobium pentaoxide, the ratio of 1:30 is by nb in molar ratio2o5After grinding uniformly with koh, anti-at 400 DEG C
2h is calcined, be dissolved in water is obtained solution containing nb to products therefrom (product is niobium oxide gel), then will under the conditions of answering
Solution containing nb and the ammonium paramolybdate aqueous solution, and mn, fe solution (mn, fe element correspondence through edta complexing
Raw material) be mixed to get mixed aqueous solution according to mol ratio 1:1:7:1, wherein, active component in solution (manganese nitrate,
Ferric nitrate, ammonium paramolybdate ((nh4)6mo7o24) and niobium pentaoxide) mass percentage concentration be 40wt%；
2) carrier is put in complex solution immersion 6h(1-6h), the complete loaded body of solution to be impregnated is inhaled
Attached, 4h is dried in 120 DEG C of (50-120 DEG C) drying boxes, then under 800 DEG C (200-800 DEG C)
Calcining 2h(2-10h), obtain scr catalyst.
Embodiment 10, preparation scr catalyst
Comprise the following steps:
1st, prepare carrier
Same as Example 2.
2nd, the load of active component
With embodiment 9 operate identical, only by ammonium paramolybdate ((nh4)6mo7o24) replace with ammonium tetramolybdate ((nh4)2mo4o13).
Embodiment 11, preparation scr catalyst
Comprise the following steps:
1st, prepare carrier
Same as Example 3.
2nd, the load of active component
Same as Example 9, only by ammonium paramolybdate ((nh4)6mo7o24) replace with ammonium tungstate ((nh4)10w12o41).
Embodiment 12, preparation scr catalyst
Comprise the following steps:
1st, prepare carrier
Same as Example 4.
2nd, the load of active component
Same as Example 9, only by ammonium paramolybdate ((nh4)6mo7o24) replace with ammonium metatungstate (nh4)6h2w12o40.nh2o.
Scr catalyst for present invention preparation is detected:
Test 1, the xrd collection of illustrative plates of scr catalyst sample of the present invention
Catalyst sample is fully ground, using German d8advance type x-ray diffraction instrument (bruker) before test
Material phase analysis are carried out to the scr catalyst sample (with embodiment 1,5,9 sample as representative) of preparation, ni filters,
Cu target, k α radiation source, scanning angle scope is 10 °～80 °, and the wavelength of x-ray is 0.15406nm.
Shown in testing result such as Fig. 1 (abscissa represents the angle of diffraction, and ordinate represents diffracted intensity), in each catalyst
Diffracting spectrum in only it is observed that carrier anatase crystal tio2(jcpds:21-1272) typical diffractive peak
(2 θ=25.55 °, 37.15 °, 48.35 °, 54.15 ° and 55.35 °), do not observe the diffraction of active component
Peak, shows that active component is dispersed in carrier surface with amorphous state.
The diffraction maximum of active component is not equally observed in the diffracting spectrum of other embodiments sample.Here does not arrange one by one
Show.
Test 2, detection scr catalyst of the present invention are to the denitrating flue gas effect after cement kiln tail deduster
Low-temperature denitration of flue gas after deduster for the cement kiln exit gas, the main component of described low-temperature flue gas includes
o2、co2、nox, a small amount of so2And vapor, and contain a small amount of dust granules and alkali metal impurity, now
Generally below 120 DEG C of flue-gas temperature；In the present invention, scr catalyst is carried out by experiment to the denitration effect of low-temperature flue gas
Test.Experimental provision and workflow as shown in Fig. 2 experimental provision used include gas bomb 1, flowmeter 2,
Blender 3, quartz reactor 4, temperature controller 5, beds 6, thermocouple 7, flue gas analyzer 8 and
Computer 9.
Flue gas adopts standard steel cylinder gas to simulate, and flue gas consists of no(600 × 10-6), nh3(600 × 10-6), o2
(6%), n2For carrier gas, air speed is 10000h-1, total gas flow rate is 833ml/min, the filling of catalyst sample
Volume is 5ml.Catalyst activity test is carried out in fixed bed quartz ampoule scr reactor 4, and quartz ampoule specification is
φ 8mm × 1000mm, using external electric pattern, catalyst bed 6 temperature is by tube type resistance furnace control.Survey respectively
The no removal efficiency of fixed 80 DEG C, 100 DEG C, 125 DEG C, 150 DEG C, 175 DEG C, 200 DEG C, 250 DEG C etc. 7 temperature spots,
After each temperature spot all stably reacts 10min, before measuring reaction using flue gas analyzer (testo350, Germany) 8
No concentration in gas afterwards.Wherein, no conversion ratio (%)=[(noin-noout)/noin] × 100%.
Test the catalyst activity curve such as Fig. 3 (abscissa represents test temperature, and ordinate represents no conversion ratio) obtaining
Shown it can be seen that three kinds of catalyst (with embodiment 1,5,9 sample as representative) are respectively provided with higher denitration activity,
Reach 70% about efficiency when 80 DEG C.With the rising of reaction temperature, the activity of catalyst significantly increases.
When 125-200 DEG C, denitration performance is more than 90%, and has wider active temperature windows.On temperature continues
Rise, when reaching 250 DEG C, the efficiency of denitration decreases.
Other embodiments sample is also done with same test, the catalyst activity curve that test obtains is similar with Fig. 2, does not have
There is substantial difference, for this reason not offer curves one by one.
Test 3, the test of anti-Poisoning
In the present invention, scr catalyst is tested by experiment to the anti-poisoning performance of cement kiln low-temperature flue gas.Experiment dress
Put and workflow as shown in figure 4, experimental provision used include multiple gas bombs 1, flowmeter 2, humidifier 3,
Heater 4, blender 5, thermometer 6, quartz reactor 7, temperature controller 8, beds 9, thermoelectricity
Even 10, flue gas analyzer 11 and computer 12.
Flue gas adopts standard steel cylinder gas to simulate, and flue gas consists of no(600 × 10-6), nh3(600 × 10-6), o2
(6%), so2(100 × 10-6), n2For carrier gas, air speed is 10000h-1, total gas flow rate is 833ml/min,
The volume fraction of water vapour is 10%, and the admission space of catalyst sample is 5ml.The temperature controlling water in humidifier can
To change h in gas2The volume fraction of o.It is not added with h in reaction gas2O and so2When, correspondingly by water in humidifier bottle
Pour out, by so2The valve closing of steel cylinder.Catalyst activity test is carried out in fixed bed quartz ampoule scr reactor 7,
Quartz ampoule specification is φ 8mm × 1000mm, and using external electric pattern, catalyst bed temperature is by tube type resistance furnace control
System.At measuring 175 DEG C, it is passed through h2O and so2In front and back, the no removal efficiency to cement kiln low-temperature flue gas for the catalyst.
Measure the no concentration in gas before and after reacting using flue gas analyzer (testo350, Germany) 11.Wherein, no turns
Rate (%)=[(noin-noout)/noin] × 100%.
Fig. 5 shows catalyst so at 175 DEG C of reaction temperature2And h2Low temperature active when o coexists it can be seen that
It is simultaneously introduced 100 × 10 in flue gas-6so2After 10% (ψ) water vapour, each catalyst is (with embodiment 1,5,9 sample
Product are representative) although denitration performance decrease, less, no removal efficiency still reaches more than 85%, shows for change
The scr catalyst of the present invention has higher sulfur resistive and vapour resistant performance.
Other embodiments sample is also done with same test, the catalyst activity curve that test obtains is similar with Fig. 5, does not have
There is substantial difference, for this reason not offer curves one by one.
Claims (12)
1. a kind of scr catalyst for cement kiln tail low-temperature denitration of flue gas, be active component is supported on cellular
Carrier on prepare, described active component be manganese with selected from tungsten (w), molybdenum (mo), iron (fe), copper (cu),
The combination of the multiple element in cerium (ce), lanthanum (la), bismuth (bi), niobium (nb) and tantalum (ta)；
Manganese (mn), iron (fe), copper (cu), cerium (ce), lanthanum (la), bismuth (bi) presoma be chlorate or
Acetate, the presoma of niobium (nb) and tantalum (ta) is oxide niobium pentaoxide (nb2o5) or tantalum pentoxide (ta2o5),
Tungsten (w) is ammonium molybdate, ammonium paramolybdate, ammonium tetramolybdate, ammonium tungstate, ammonium metatungstate with the presoma of molybdenum (mo)；
Described carrier is: by titanium dioxide (tio2), alchlor (al2o3) and zirconium dioxide (zro2) in many
Plant the powder assembling and h2O, cmc (hydroxymethyl cellulose), mea (monoethanolamine) according to 100:10:1:1 quality
Ratio is mixed, agglomerating, after extrusion molding, dries, then obtains after calcining 4-6h at 1000 DEG C.
2. scr catalyst according to claim 1 it is characterised in that: active component accounts for including carrier
Catalyst total quality percentage be 5wt%-25wt%.
3. scr catalyst according to claim 2 it is characterised in that: active component accounts for including carrier
Catalyst total quality percentage be 5wt%-15wt% or 15wt%-25wt%.
4. the scr catalyst according to claim 1 or 2 or 3 it is characterised in that: manganese (mn) element accounts for
The molar percentage of the total element of active component is 60%-95%.
5. scr catalyst according to claim 4 it is characterised in that: manganese (mn) element accounts for active component
The molar percentage of total element is 70%-90%.
6. scr catalyst according to claim 3 it is characterised in that: each element mole hundred in active component
Ratio is divided to be respectively as follows:
Above each element multiple combination in the range of being limited uses, the consumption of total amount and manganese (mn) 60%-95% add and
For active component total mole number 100%.
7. the scr catalyst according to claim 1 or 2 or 3 or 6 it is characterised in that: described scr catalysis
Agent has anti-so2Poisoning and steam-resistant poisoning performance.
8. scr catalyst according to claim 4 it is characterised in that: described scr catalyst has anti-so2
Poisoning and steam-resistant poisoning performance.
9. scr catalyst according to claim 5 it is characterised in that: described scr catalyst has anti-so2
Poisoning and steam-resistant poisoning performance.
10. a kind of prepare the arbitrary described scr catalyst for cement kiln tail low-temperature denitration of flue gas of claim 1-9
Method, be to load to active component by infusion process to be obtained on carrier, specifically include following steps:
1) prepare carrier
By titanium dioxide (tio2), alchlor (al2o3) and zirconium dioxide (zro2) one or more of assemble
Powder and h2O, cmc (hydroxymethyl cellulose), mea (monoethanolamine) are carried out according to the mass ratio of 100:10:1:1
Mixing, agglomerating, after extrusion molding, dry, then obtain after calcining 2-10h at 500-1200 DEG C；
2) preparation of active component mixed aqueous solution
Design loading by carrier and calculate each element forerunner's weight in required active component, prepare and contain active component
Mixed aqueous solution, make the presoma of active component in mixed aqueous solution mass percentage concentration be 5wt%-50wt%；
3) load of active component
Carrier is put in active component mixed aqueous solution immersion 1-6h, after the complete loaded body absorption of solution to be impregnated,
Dry at 50-120 DEG C, then calcine 2-10h at 200-800 DEG C, obtain scr catalyst.
The arbitrary described scr catalyst of 11. claims 1-9 is in the low temperature after deduster to cement kiln exit gas
Flue gas carries out the application in denitration.
12. apply it is characterised in that installing catalysis after the deduster of cement kiln tail additional according to claim 11
Reduction reaction device, is mounted with described scr catalyst, carries out denitration with scr catalyst to low-temperature flue gas in device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310693174.6A CN103638942B (en) | 2013-12-17 | 2013-12-17 | SCR (selective catalytic reduction) catalyst for denitrating low-temperature smoke of cement kiln and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310693174.6A CN103638942B (en) | 2013-12-17 | 2013-12-17 | SCR (selective catalytic reduction) catalyst for denitrating low-temperature smoke of cement kiln and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103638942A CN103638942A (en) | 2014-03-19 |
| CN103638942B true CN103638942B (en) | 2017-01-18 |
Family
ID=50244309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310693174.6A Active CN103638942B (en) | 2013-12-17 | 2013-12-17 | SCR (selective catalytic reduction) catalyst for denitrating low-temperature smoke of cement kiln and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103638942B (en) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923213B (en) * | 2015-06-26 | 2018-01-02 | 卓润生 | A kind of nontoxic rare-earth type denitrating catalyst and its preparation method and application |
| CN104998684B (en) * | 2015-07-10 | 2018-02-02 | 山东海润环保科技有限公司 | A kind of rare earth modified SCR denitration and preparation method thereof |
| CN105126922B (en) * | 2015-07-10 | 2018-04-03 | 山东海润环保科技有限公司 | One kind is without vanadium SCR denitration and preparation method thereof |
| CN105013540A (en) * | 2015-07-10 | 2015-11-04 | 山东海润环保科技有限公司 | Marine denitration catalyst and preparation method therefor |
| CN105056923B (en) * | 2015-08-17 | 2018-11-09 | 成都金鑫天蓝科技有限公司 | A kind of water resistant sulfur resistive type denitrating catalyst, preparation method and its usage |
| CN105363434A (en) * | 2015-11-17 | 2016-03-02 | 安徽省元琛环保科技有限公司 | Manganese based SCR catalyst for low temperature denitration and preparation method thereof |
| CN105617831A (en) * | 2015-12-31 | 2016-06-01 | 上海东化环境工程有限公司 | Flue gas low-temperature denitration and semi-dry desulfurization process |
| CN106268769B (en) * | 2016-08-26 | 2017-10-13 | 大唐南京环保科技有限责任公司 | A kind of rare-earth-based Plate-type denitration catalyst and preparation method |
| CN106238067B (en) * | 2016-08-30 | 2018-12-21 | 山东海润环保科技有限公司 | Denitration takes off VOC catalyst |
| CN106311221B (en) * | 2016-08-31 | 2019-01-11 | 中国建筑材料科学研究总院 | Low-temperature denitration catalyst and preparation method thereof with mesomorphic structure |
| CN106955698B (en) * | 2017-04-07 | 2019-05-31 | 太原理工大学 | Denitrating catalyst preparation method based on meso-porous titanium dioxide titanium carrier |
| CN109092323A (en) * | 2017-06-20 | 2018-12-28 | 中国石油化工股份有限公司 | Low-temperature SCR catalyst for denitrating flue gas and its preparation method and application |
| CN109745995B (en) * | 2017-11-03 | 2020-12-18 | 中国石油化工股份有限公司 | Wide-temperature-window SCR flue gas denitration catalyst and preparation method and application thereof |
| CN108144601A (en) * | 2018-02-05 | 2018-06-12 | 安徽弘昇环境工程科技有限公司 | A kind of SCR ultralow temperature denitrating catalyst and preparation method thereof |
| CN108380212B (en) * | 2018-03-09 | 2020-11-03 | 北京工业大学 | Inorganic porous material for denitration of cement kiln decomposing furnace flue gas and use method thereof |
| CN108525707A (en) * | 2018-04-02 | 2018-09-14 | 北京水木星源环保科技有限公司 | A kind of honeycomb type denitrification catalyst and preparation method |
| CN108333290A (en) * | 2018-04-17 | 2018-07-27 | 河北工业大学 | A kind of test device and test method of cement kiln low-temperature denitration of flue gas catalyst sulfur resistive water resistance |
| CN108543549B (en) * | 2018-04-19 | 2020-12-29 | 南京信息工程大学 | Regeneration method of dedusting and denitration multifunctional filter material |
| CN108620078B (en) * | 2018-05-09 | 2022-01-04 | 淄博鹏达环保科技有限公司 | Catalyst, preparation method of catalyst and method for denitration of coal combustion high-temperature flue gas |
| CN109211884A (en) * | 2018-11-08 | 2019-01-15 | 广西玉柴机器股份有限公司 | A kind of chemiluminescent analyzer NOx conversion efficiency rapid detection method |
| CN112569777A (en) * | 2019-09-27 | 2021-03-30 | 富利康科技股份有限公司 | Water-gas resistant denitration device and catalyst suitable for low-temperature environment |
| CN112570020B (en) * | 2019-09-29 | 2023-07-18 | 中石化南京化工研究院有限公司 | Desulfurization and denitrification catalyst and preparation method thereof |
| CN111111647B (en) * | 2020-01-19 | 2021-11-16 | 北京科技大学 | Niobite type manganese-niobium-based SCR denitration catalyst and preparation method thereof |
| CN111905716B (en) * | 2020-07-31 | 2021-09-24 | 江苏龙净科杰环保技术有限公司 | Thallium poisoning resistant core-shell honeycomb catalyst for cement kiln flue gas denitration and preparation method thereof |
| CN112642438A (en) * | 2020-12-21 | 2021-04-13 | 中国建筑材料科学研究总院有限公司 | Catalyst composition, SCR catalyst and preparation method thereof, in-situ regenerated catalyst and preparation method and regeneration method thereof |
| CN112844424B (en) * | 2020-12-30 | 2022-05-17 | 山东天璨环保科技有限公司 | Low-temperature denitration catalyst and preparation method thereof |
| CN113244930A (en) * | 2021-02-24 | 2021-08-13 | 南京大学 | Mn-based catalyst for low-temperature denitration and preparation method and application thereof |
| CN113198487A (en) * | 2021-05-07 | 2021-08-03 | 南京宏硕环保新材料科技有限公司 | Low-temperature denitration catalyst and preparation method thereof |
| CN113926448B (en) * | 2021-11-01 | 2023-07-25 | 华北电力大学（保定） | Niobium oxide-loaded catalyst and method for catalyzing and degrading dimethyl sulfoxide by using same |
| CN114192138A (en) * | 2021-12-31 | 2022-03-18 | 上海大学 | Low-temperature metal oxide catalyst resisting hydrothermal aging and preparation method thereof |
| CN114602493A (en) * | 2022-04-12 | 2022-06-10 | 山东亮剑环保新材料有限公司 | Zirconium-based-rare metal denitration catalyst and production method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103263913B (en) * | 2013-04-27 | 2015-03-04 | 北京工业大学 | Preparation method for high-specific surface anti-alkalosis denitration catalyst applicable to cement kiln |
-
2013
- 2013-12-17 CN CN201310693174.6A patent/CN103638942B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103638942A (en) | 2014-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103638942B (en) | SCR (selective catalytic reduction) catalyst for denitrating low-temperature smoke of cement kiln and preparation method thereof | |
| CN101898136B (en) | Titanium-based multi-metal oxide catalyst for removing diesel engine NOx by NH3-SCR in wide temperature window | |
| CA2545332C (en) | Exhaust gas catalyst | |
| CN100542670C (en) | Low temperature multicomponent catalyst in a kind of denitrating flue gas and preparation method thereof | |
| CN101396655A (en) | Titanium-base multi-component catalyst for power plant flue-gas SCR denitration and preparation method thereof | |
| CN101676019B (en) | Catalyst for low-temperature denitration of power-plant flue gas by selective catalytic reduction (SCR) and preparation method thereof | |
| MX2011010613A (en) | Transition-metal vanadate or mixed transition-metal / rare earth vanadate based catalyst composition for selective catalytic reduction of exhaust gases. | |
| CN101507928A (en) | Ferro manganese composite oxides catalyst and preparation method and use thereof | |
| WO2008150462A2 (en) | Catalyst for selective reduction of nitrogen oxides, method for making same and use thereof | |
| CN101396656A (en) | Power plant flue-gas SCR denitration catalyst capable of preventing sulfur trioxide poisoning and preparation method thereof | |
| CN105771961B (en) | A kind of CeO2Nanotube supported denitrating catalyst and preparation method thereof | |
| CN105363494A (en) | SCR denitration catalyst and preparation method thereof | |
| CN101422736A (en) | Catalyst for removing nitrogen oxide in FCC stack gas at low temperature and production method thereof | |
| CN102600832A (en) | Combined catalyst for improving denitration performance and application thereof | |
| CN104307564A (en) | Auxiliary agent doped Cu-SAPO-34 catalyst, preparation method and applications thereof | |
| CN106861676A (en) | A kind of anti-sulfur dioxide is suitable to denitrating catalyst that low temperature is used and preparation method thereof | |
| CN109701524A (en) | Remove the catalyst and preparation method thereof of nitrogen oxides | |
| CN108671946A (en) | Phosphorus doping cerium titanium catalyst, preparation and its application in selective-catalytic-reduction denitrified | |
| CN111229305A (en) | Molybdenum-modified Fe-ZSM5 molecular sieve catalyst, and preparation method and application thereof | |
| YAN et al. | Lead poisoning and regeneration of Mn-Ce/TiO2 catalysts for NH3-SCR of NOx at low temperature | |
| CN101554589A (en) | Copper and iron modified titanium dioxide pillared bentonite catalyst and preparation method thereof | |
| CN104923213B (en) | A kind of nontoxic rare-earth type denitrating catalyst and its preparation method and application | |
| WU et al. | Effect of preparation methods on denitration performance of V-Mo/TiO2 catalyst | |
| US11371406B2 (en) | Low-temperature de-NOx catalyst for treatment of exhaust gas from stationary source and method of manufacturing same | |
| Feng et al. | Niobium oxide promoted with alkali metal nitrates for soot particulate combustion: elucidating the vital role of active surface nitrate groups |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |